THE EFFECT OF POLYMERIZATION

TEMPERATURE ON POLYURETHANE SYNTHESIS

USING NYAMPLUNG (Calophyllum inophyllum) OIL-
BASED POLYOLS Commented [Reviewer1]: English must be improved

Abstract. Generally, polyurethane was synthesized using polyol as raw materials, derived from non-renewable petroleum.
The demand for petroleum is increasingly high, so vegetable oil is the best alternative to replace it. This article describes
the synthesis of polyurethane using nyamplung (Calophyllum inophyllum) oil-based polyols. The polyol is reacted with Commented [Reviewer2]: polyurethane synthesis
2,4-Toluene diisocyanate at various polymerization temperatures to form polyurethane. The characteristics of the resulting
polyurethane, in general, the higher the polymerization temperature the harder and more brittle it is. At a polymerization
temperature of 70-100°C, polyurethane can be formed into a film with a smooth surface, but the higher the temperature,
the harder and brittle the film formed becomes, as indicated by a decrease in the elongation percentage, from 43.3 to 18.9%.
Meanwhile, at a polymerization temperature of 110-150°C, polyurethane forms hard foam, the higher the temperature, the
harder and stiffer it becomes. Meanwhile, at a polymerization temperature of 110-150°C polyurethane forms foam, the
higher the temperature the harder and stiffer it is.

Keywords: Polyurethane, Nyamplung (Calophyllum inophyllum) oil-based polyols, Swelling index

INTRODUCTION
Polyurethane (PU) is a versatile polymer that has several important properties, including high mechanical strength
and chemical resistance [1]. Currently, PU accounts for approximately 5% of the global polymer market and is the
sixth most widely used group of polymers [2]. PU is widely used, due to its combination of physical properties, namely
elongation, hardness, strength and modulus. Applications of PU due to the combination of these physical properties
are as biomedical applications, textiles and construction [3]. Other uses of PU are as multipurpose adhesives,
elastomers, coatings, sensors and biomedical equipment, such as contact lenses and blood oxygenators [4].
Conventionally, the polymer industry is a petrochemical-based industry, that is, an industry whose raw materials
come from petroleum. The high use of oil as a fuel and its non-renewable sources cause the availability of petroleum
to decrease. In addition, petrochemical-based polymers are polymers that are difficult to decompose by
microorganisms, in other words these polymers are not environmentally friendly. The chemical reaction underlying
PU synthesis is the addition reaction between the hydroxyl group (−OH) of diol or polyol and the isocyanate group
(−NCO) of di/poly isocyanate. In the polymer industry, both of these compounds are petrochemical-based. To reduce
dependence on petroleum and minimize the impact on the environment, research is focused on using polyols made
from local vegetable oil, namely nyamplung oil. The use of nyamplung oil as a raw material for polyols is because
this oil contains more than 50% of unsaturated fatty acids: oleic acid (46-48%) and linoleic acid (21-25%) [5]. Commented [Reviewer3]: The reference for nyamplung
The main component of PU is polyol and isocyanate. Variations in the type of polyol and isocyanate used can is still lack, please explore this
cause drastic changes in the properties of the polyurethane. The chemical structure of polyols and isocyanates imparts
the properties of softness, flexibility or hardness to the final product. Apart from the type of polyol and isocyanate,
the polymerization temperature also influences the physical properties of the PU formed. Therefore, this article
describes the effect of temperature on the synthesis of PU from polyol based on nyamplung oil and 2,4 -toluene
diisocyanate (TDI) as an isocyanate source. The parameters measured are the tensile strength and swelling
index/degree of PU. Commented [Reviewer4]: This purpose of this research
is not clear, please carefully explain this aim and purposes
 EXPERIMENTAL SECTION

Materials and Instrument Commented [Reviewer5]: Add purity for all chemical
reagents
The material used is nyamplung oil which is extracted from nyamplung seeds and purified using a method
developed by Suhendra et al., 2019 [5]. All chemicals used are analytical grade, purchased from Merck, Germany,
and used as received. These chemicals are n-hexane, 30% of hydrogen peroxide, methanol, 98% of formic acid, 97%
of sulfuric acid, bentonite, sodium bicarbonate, sodium thiosulphate, potassium iodide, chloroform, potassium
hydroxide, acetic acid anhydrous and 2, 4-toluene diisocyanate (TDI). The instruments used were a rotary evavorator
(B-ONE RE-1000VN, China), water bath stirrer (Biosan W-4 MS, England), Digital High-Temperature Oil Bath
(Daihan Scientific, Korea), Tensilon RTG-1310 (Japan) , and FTIR Spectrophotometer (Perkin Elmer FTIR–Frontier,
Waltham, MA, USA).

Epoxidation and Hydroxylation of Nyamplung Oil Procedure

This procedure was developed by Suhendra et al., (2023) [6] with slight modifications. Epoxidation Process: A
total of 60 mL of 98% formic acid, 30 mL of 30% H 2O2, and 2 mL of 97% H 2SO4 were slowly put into a three-neck
flask while stirring for 1 hour. Then, as much as 50 mL of nyamplung oil was added to the mixture and the temperature
was maintained at 40-50˚C. The reaction lasted for 2 hours. Then, the reaction mixture was left for 24 hours to separate
the oil phase from the water phase. After being separated, distilled water is added to the oil phase to remove residual
acetic acid and catalyst. Furthermore, the remaining water in the oil phase was removed using anhydrous magnesium
sulfate. Hydroxylation Process: Into the purified epoxidized oil, 150 mL of diethyl ether was added and stirred until
it dissolved. Then, 25 mL of 2 M NaOH and 25 mL of distilled water were added, stirred until two layers were formed.
After being separated, 25 mL of hot distilled water (90-100ºC) was added to the organic phase, the remaining distilled
water was evaporated using a rotary evaporator and anhydrous Na2SO4 was added and then filtered. The polyol
formed was characterized using an FTIR spectrophotometer and the polyol conversion percentage was calculated.

Synthesis of Polyurethane
This synthesis procedure uses a modified method developed by Pongmuksuwan and Harnnarongchai (2022) [7].
The polymerization process is carried out in one stage and without solvents. A total of 9.8 mL of polyol was mixed
with 2 mL of glycerol, stirred using a mechanical stirrer at a speed of 250 -260 rpm. The reaction temperatures were
set at 70, 80, 90, 100, 110, 120, 130, 140 and 150C. When the desired temperature was reached, 4 mL of TDI was
added while continuing to stir for 5 minutes. The shaped polyurethane is poured into the mold and allowed to set until
it hardens.

Hydroxyl Value Determination

Determination of the hydroxyl value of polyols was carried out using the method developed by Ghodkea at al.,
(2021) [8]. A total of 1 g of sample and 2 mL of acetylation reagent were placed in a 3-neck flask, then heated to 90°C
for 2 hours, then cooled to room temperature. Place in an Erlenmeyer and add 3 mL of distilled water, leave for 24
hours. Add 3 drops of 1% phenolphthalein and titrate with 0.5 N KOH solution. The hydroxyl number is determined
using equation below:

(𝑚𝐿 𝐾𝑂𝐻 𝑏𝑙𝑎𝑛𝑘 − 𝑚𝐿 𝐾𝑂𝐻 𝑝𝑜𝑙𝑦𝑜𝑙)𝑥 𝑁𝑥56.1

𝐻𝑦𝑑𝑟𝑜𝑥𝑦𝑙 𝑉𝑎𝑙𝑢𝑒 =
𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑝𝑜𝑙𝑦𝑜𝑙

Determination of Swelling Index

 The Swelling index (SI) of PU was determined using a method developed by Jha est al., (2022) [9]. A total of 0.2
g of the PU was placed in a petri dish and soaked in 25 mL of distilled water. After 24 hours, swelled PU was weighed
and SI was determined using equation below:

(𝑤2 − 𝑤1 ) 𝑥 100 Commented [Reviewer6]: Please add the information for

𝑆𝐼(%) =
𝑤1 abbreviation, w1, w2, and w

Tensile Strength Test

Tensile strength is a very important mechanical property of polymers, namely how much a material can withstand
a given force. The tensile strength test was carried out using ASTM D638-14 [10]. Percent Elongation, the ratio of
maximum elongation with original gage length, is calculated using the equation below:

𝐹𝑖𝑛𝑎𝑙 𝑔𝑎𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ − 𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑔𝑎𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ

𝑃𝑒𝑟𝑐𝑒𝑛𝑡 𝐸𝑙𝑜𝑛𝑔𝑎𝑡𝑖𝑜𝑛 = 𝑥 100
𝑂𝑟𝑖𝑔𝑖𝑛𝑎𝑙 𝑔𝑎𝑔𝑒 𝑙𝑒𝑛𝑔𝑡ℎ

Characterization

Several tests have been carried out to ensure that all reactions proceed as desired, including determining oxirane
oxygen content (OOC), measuring iodine value (IV), and determining relative conversion to oxirane (RCO).
Characterization of the product was carried out by analyzing the Fourier Transform Infrared (FTIR) spectrum. Spectra
were recorded using a Perkin-Elmer Model Frontier FTIR spectrophotometer (Perkin-Elmer, USA). Commented [Reviewer7]: Please add detail for the
experimental conditions

RESULTS AND DISCUSSION

Synthesis of Polyol
Synthesis of polyurethane starts from the epoxidation reaction of nyamplung oil followed by a hydroxylation
reaction to form nyamplung oil polyol simultaneously (Scheme 1).
 SCHEME 1. Epoxidation and hydroxylation of triglyceride [11, 12] Commented [Reviewer8]: Please indicate which part is
epoxidation and hydroxylation
The formation of oxirane/epoxy rings in oil is caused by the oxidation of the double bonds of the fatty acids of
nyamplung oil through an epoxidation reaction. In general, the oil epoxidation reaction is the conversion of unsaturated
bonds in the fatty acid chain into oxirane rings caused by organic acids. In this epoxidation of nyamplung oil, formic
acid is used as an oxygen acceptor and hydrogen peroxide as an oxygen donor. This reaction is an in situ reaction and
sulfuric acid is used as a catalyst, where the performic acid formed then reacts with the double bonds in the fatty acid
to form an oxirane ring [13] (Gunawan et al., 2023). The purpose of adding sulfuric acid is to accelerate the equilibrium
formation of performic acid. However, the more H+ ions there are, the easier the oxirane ring formed will open again.
Therefore, in polyol synthesis sulfuric acid is used as a catalyst. The process of opening the oxirane/epoxy ring by
water begins with the protonation of the oxygen atom in the oxirane ring by H + ions from the sulfuric acid catalyst.
Once the carbon-oxygen bond opens, positive charges accumulate on the substituted carbon atom. Next, the
nucleophile (from water) attacks the substituted carbon atom. The final stage of this process is oxygen deprotonation
to form polyol [14] (Kamairudin et al., 2021).

Characterization of Polyol
In the field of chemistry, iodine value (IV) is defined as the weight of iodine in grams that reacts with 100 grams
of a chemical. IV is a measure of unsaturation in fats, oils, or waxes. The difference in the iodine value of the
nyamplung oil and the product indicates that the double bonds in the fatty acid chain of the oil have been broken and
polyols have been formed. In this study, the iodine value of nyamplung oil was 63.45 g iodine/ 100 g, while the iodine
value of the product (polyol) was 8.46 g iodine/ 100 g. This significant decrease in iodine value indicates that there
has been a break in the double bond (-C=C-) in the fatty acid chain to form polyol with a conversion percentage of
86.67%. The presence of IV in the product indicates that there are still double bonds in the fatty acid chain.
Other data that supports the formation of polyols is the hydroxyl value (HV). The HV of an oil is an indication of
the presence of hydroxyl groups in the fatty acid chain [15]. In this study, the HV obtained was 57.97 mg KOH/g.
Apart from HV, the FTIR spectrum of the product (Fig. 1) also supports the formation of polyols. Figure 1 shows the
absorption at 3750-3000 cm-1 which is the typical absorption of the OH group. In the product spectrum there is also
no visible absorption at 3000-2900 cm-1 which is the typical absorption of the =C-H group. The disappearance of =C-
H absorption and the presence of OH absorption indicates that polyol has been formed.

Figure 1. FTIR spectrum of nyamplung oil and polyol Commented [Reviewer9]: Axis -X must be written as
wavelength

Synthesis of Polyurethane
Polyurethane contains urethane bonds (-NHCOO-) which are formed from the reaction between the isocyanate
group (-NCO) and the hydroxyl group (-OH). PU is classified as a type of copolymer which consists of soft and hard
segments. Soft segments contribute elasticity to the polymer, while hard segments contribute strength and stiffness
through physical cross-linking points. The soft segment is usually in the form of polyether or polyester polyol, while
the hard segment consists of diisoanate and chain extender [16].
In this research, PU was synthesized by reacting nyamplung oil based polyol and 2,4-TDI, and adding glycerol as
a chain extender which can increase the length of the hard segment. Heating aims to reduce the viscosity of the polyol
and increase the mass transfer factor, making it easier to mix and react with the isocyanate (Scheme 2). In other words,
heating affects the relative number of hard and soft segments, which ultimately affects the mechanical properties of
PU [17, 18].
 Commented [Reviewer10]: Please provde with HR

Scheme 2. Soft and hard segments on PU [19]

Analysis of the polyol and product spectrum (Fig. 2) shows that there is an absorption at wave number 3500-3000
cm-1 which is a typical absorption of secondary N-H and is supported by an absorption at 1383 cm -1, which is a typical
absorption of C-N. The absorption at the wave number 2267 cm -1 is a typical absorption for the C=O urethane group
and is supported by the absorption at 1617 cm -1.
 Figure 2. FTIR spectrum of polyol and product

Characteristic of PU

In this research, PU produced at a temperature variation of 70-100C was in the form of a film with a smooth
surface, while PU at a temperature variation of 110-150C was in the form of a dense and stiff foam (Fig. 3).

70C 80C 90C

100C 110C 120C

 130C 140C 150C
Figure 3. PU of various temperatures

One of the parameters that can be used to determine low or high cross-linking in a polymer is swelling
index/swelling degree/swelling capacity which is defined as the amount of a liquid that can be absorbed or entrapped
within the porous surface of a polymer. The higher the swelling index of a polymer, the lower the cross-linking in the
polymer chain [20]. In this study, the swelling index of the product decreased as the polymerization temperature
increased (Fig. 4). This shows that the higher the reaction temperature, the higher the cross-linking in PU.

25

20
Swelling index, %

15

10

0
70 80 90 100 110 120 130 140 150
Temperature, C

Figure 4. Plot swelling index of the product Commented [Reviewer11]: How did authors determine
the swelling index for high temperature? I am wondering it
Another parameter commonly used to determine the mechanical properties of polymers is the tensile strength will be difficult because you got the powder materials
test/tensile test (TT). TT is used to determine the maximum load that can be withstood by a material or product, the
test of which is based on the load value or elongation value. The mechanical properties of polymers are often expressed
in terms of stress (force per unit area) and strain (percent change in length). Stress is obtained by dividing the applied
force by the cross-sectional area of the sample. Meanwhile, strain is obtained by dividing the change in length by the
initial length of the sample (ε = ∆L/L). Testing and measuring procedures vary based on the material being tested and
its intended application.
 50

40

30
Elongation, %

20

10

0
70 80 90 100

Temperature, °C

Figure 5. Tensile test of PU

In this research, the tensile strength test was carried out based on the elongation value, namely the sample was
pulled to the breaking point. The tensile strength test was carried out using the ASTM D638 -14 procedure on PU in
film form, namely PU produced at a polymerization temperature of 70-100C. Figure 5 shows that the higher the
polymerization temperature of PU, the lower the elongation value. This is proof that the higher the polymerization
temperature, the higher the cross-links formed and the stronger the PU produced.

CONCLUSION
Polyurethane has been successfully synthesized through the polymerization reaction of 2, 4-toluene diisocyanate
and nyamplung oil based polyol. The formation of polyurethane is indicated by absorption at wave numbers 3500-
3000 cm-1 and 2267 cm-1 which are typical absorptions, respectively, from secondary N-H and C=O groups of
urethane in the FTIR spectrum of the product. From the swelling index and elongation percentage data, it is known
that the higher the polymerization temperature, the harder the polyurethane that is formed is due to the higher
polyurethane cross-link density.

ACKNOWLEDGMENTS

This research was funded by the Ministry of Education, Culture, Research and Technology of Republic of Indonesia,
through the 2023-2024 National Basic Research Scheme.

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